KR20160010566A - Method for producing polyamide composite materials containing silicon - Google Patents

Abstract

화학식 (A)에서, m은 1 ∼ 11, 특히 2 ∼ 9의 정수, 특히 3을 나타내고, #은 화합물(SV)의 규소 원자에 대한 연결점을 나타낸다.The present invention relates to a process for producing a silicon-containing polyamide composite, comprising the steps of: a) reacting a silicon-containing polyamide composite material having at least one silicon atom with at least one lactamyl group of formula (A) Comprising the copolymerization of at least one silicon compound (SV); b) The process also comprises copolymerization with one or more comonomers (CM) selected from ammonium salts of dicarboxylic acids, amino acids, amino acid amides and lactams:

In the formula (A), m represents an integer of 1 to 11, particularly an integer of 2 to 9, particularly 3, and # represents a connecting point to the silicon atom of the compound (SV).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of producing a polyamide composite material containing silicon,

The present invention relates to a method for producing a silicon-containing polyamide composite material (hereinafter also referred to as a polyamide-silicon composite material), a composite material obtainable by the method, and a use thereof.

Polyamides are polymers that are produced on a large scale around the world and are mainly used for fibers, industrial polymers and films / sheets, and for many other purposes. Nylon-6 is the most polyamide produced, accounting for about 57% of total polyamide production.

A composite material based on polyamide (hereinafter also referred to as a polyamide composite material) is usually produced by incorporating a generally inorganic filler finely divided into a polyamide matrix. The polyamide composite can also be obtained by polymerizing the monomers in the presence of a finely divided filler.

Fillers in polyamide matrices can confer various improved or even new properties to the original polyamide (A. Yebra-Rodriguez et al., Appl. Clay Sci. 2009, 43, 91-97). Silicon dioxide is perhaps the best known and most commonly used inorganic filler. This undoubtedly significantly improves the mechanical and thermal properties of the polyamide.

However, uniform incorporation of the filler in the polyamide always requires some chemical modification of the filler.

US 4,739,007 describes the preparation of a polyamide-silicon composite with a two-step process wherein a chemically modified sheet-silicate, e. G. A montmorillonite pretreated with a swelling agent, is first incorporated into the monomer melt, . The resultant composite material has high mechanical strength and excellent high-temperature characteristics, and contains a silicate component in the form of a peeled layered silicate dispersed in a polymer matrix.

F. Yang et al., J. Appl. Polym. Sci. 1998, 69, 355-361 describes a process for producing a polyamide-silicon composite wherein a suspension of aminobutyric acid-modified silica is polymerized in epsilon -caprolactam to form nylon-6 .

S. S. et al. Mohamadi et al., J. Nanosci. Nanotechnol. 2009, 9, 3959-3965 describes a similar process for preparing polyamide-silicon composites by polymerizing a caprolactam melt comprising chemically modified montmorillonite.

US 6136908, US 2005256244, US 6,906,127, US 6,057,396 describe a two-step process for preparing a silicon-containing polyamide composite wherein the polyamide-forming monomers, such as lactam monomers, are first cast onto a swellable sheet- Intercalated monomers are polymerized in a second step to form a nanocomposite comprising a silicate layer dispersed in a thermoplastic polymer matrix.

All existing methods of making polyamide composites are based on incorporation of chemically modified fillers that are finely divided into monomers that form the polyamide melt or polyamide. This causes all the series of problems, in particular the non-uniformity of the resulting polymer composite, but also causes the difficult handling of the sheet-silicate, e.g. the risk of re-aggregation of the sheet-silicate upon incorporation into the monomer, to be capped. In addition, the materials used to modify the filler often adversely affect product quality, such as product color or product stability. Finally, the handling of powder materials poses a health risk.

Despite numerous improvements and developments in the manufacture of polyamide-silicon composites, the problems described herein have hitherto prevented the use of polyamide-silicon composites on a large industrial scale.

There have been various reports on a method for producing a silicon-containing composite material by twin polymerization. However, only composite materials based on phenolic resins or polypurfuryl resins can be obtained by this method (see, for example, S. Spange, S. Grund, Adv. Mat. 2009, 21, 2111- 2116 und S. Spange et al, Angew Chem 2009, 121, 8403-8408;...... Angew Chem Int see Ed 2009, 48, 8254-8258)] ..

An object of the present invention is to provide a process for producing a silicon-containing polyamide composite material, in which the above-mentioned disadvantages are avoided. More specifically, this method will enable the production of polyamide-silicon composites in a one-port reaction, without the costly and cumbersome addition of chemically modified powdered inorganic fillers, i.e., Amide composite material.

Surprisingly, this and other objects are achieved by a process for the preparation of a compound of formula (I) which comprises at least one silicon compound (SV) comprising at least one silicon atom containing one or more lactamyl radicals attached via a nitrogen atom and having the formula , An aminocarboxylic acid and / or an ammonium salt of a dicarboxylic acid and / or a lactam.

In the formula (A), m is an integer of 1 to 11, particularly an integer of 2 to 9, especially 3, and # denotes the point of attachment of the compound SV to the silicon atom.

Accordingly, the present invention provides a method for producing a silicon-containing polyamide composite material,

a. At least one silicon compound (SV) comprising at least one silicon atom containing at least one lactamyl radical attached through a nitrogen atom and having the formula (A)

b.  At least one comonomer (CM) selected from an ammonium salt of a dicarboxylic acid, an aminocarboxylic acid, an aminocarboxamide and a lactam,

Wherein at least one comonomer (CM) is selected such that water is produced during copolymerization or that water is added to the copolymerization reaction.

The process of the present invention differs from known processes of the prior art in that silicon can be incorporated directly into the polymerization in the form of a monomer-soluble compound. The use of chemically modified powdered fillers and the problems associated therewith, such as lack of ease of handling and health risks, can be ruled out in this manner. Also, the risk of contamination by impurities in the natural silicate is reduced.

The method of the present invention is also notable in that the silicon component in the resulting composite material forms a more uniform dispersion in the polyamide matrix than is possible when using the powder filler. Thus, the silicon-containing polyamide composites obtainable according to the present invention are novel and also form part of the subject matter of the present invention.

Described later in the description of the invention.

Composite synthesis is believed to proceed through coupled twin polymerization (which represents a new type of twin polymerization), such as the twin polymerization described by Spange et al. Hereinafter, for the sake of simplicity, only the term "copolymerization" will be used. A decisive feature of the twin polymerization is that polymerization of one twin monomer produces both an organic homopolymer and an inorganic homopolymer. In some cases, such as those described by Spange et al., Twin polymerization occurs with the release of water, but consumes water in this case. Since both polymers, i.e., polyamide and silicon oxide polymer, are formed nearly simultaneously, both are generally present as very fine dispersions, wherein the dimensions of the domains on the polymer are generally nanometer sizes, e.g., 1000 nm or less, Or even 200 nm or less.

The terms used in the organic groups to define the formulas herein and in the following, such as "alkyl", "alkoxy", "alkenyl", and "aryl" collectively refer to each member of the group of these organic units. The prefix C _x -C _y represents the number of carbon atoms that may be present in a particular case.

The term "C ₁ -C ₆ -alkyl" refers to saturated, straight or branched chain hydrocarbyl groups of 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, such as methyl, ethyl, Methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, Butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2- ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl , 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and isomers thereof. C ₁ -C ₄ -alkyl includes, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

The term "optionally substituted C ₁ -C ₆ -alkyl" is an unsubstituted C ₁ -C ₆ as defined above, - a C ₁ -C ₆ substituted alkyl, or one of the hydrogen atoms is substituted-alkyl, such as For example C ₁ -C ₄ -alkoxy, phenyl or C ₃ -C ₆ -cycloalkyl.

The term "C ₂ -C ₆ -alkenyl" refers to an unsaturated, straight or branched chain hydrocarbyl group of 2 to 6 carbon atoms, especially 2 to 4 carbon atoms, such as ethenyl (= vinyl) Propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, Phenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, Methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3- Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, Propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, , 4-methyl-2-pentenyl, 1-methyl-3 Methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl- Methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, Butenyl, 1,3-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, Butenyl, 2,3-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3- 1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2- Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl- Ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl.

The term "optionally substituted C ₁ -C ₆ - alkenyl", unsubstituted as defined above, C ₁ -C ₆ - alkyl, or one of the hydrogen atoms is substituted with a substituent C ₁ -C ₆ - alkyl, For example C ₁ -C ₄ -alkoxy, phenyl or C ₃ -C ₆ -cycloalkyl.

The term "C ₁ -C ₆ - alkoxy" refers to a saturated alkyl of straight or branched chain containing 1 to 6 carbon atoms and which is attached via an oxygen atom. Examples include C ₁ -C ₆ -alkoxy such as methoxy, ethoxy, OCH ₂ -C ₂ H ₅ , OCH (CH ₃ ) ₂ , n-butoxy, OCH (CH ₃ ) -C ₂ H ₅ , OCH ₂ But are not limited to, -CH (CH ₃ ) _2, OC (CH ₃ ) ₃ , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, Dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, Dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, , 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy and the like.

The term "optionally substituted C ₁ -C ₆ - alkoxy" is unsubstituted C ₁ -C ₆ as defined above, - an alkoxy, for example, - alkoxy, or one of the hydrogen atoms is substituted with a substituent C ₁ -C ₆ For example C ₁ -C ₄ -alkoxy, phenyl or C ₃ -C ₆ -cycloalkyl.

The term "C ₃ -C ₈ -cycloalkyl" denotes a monocyclic or bicyclic, saturated hydrocarbyl radical comprising 3 to 8, in particular 3 to 6 carbon atoms. Examples of monocyclic radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Examples of bicyclic radicals include bicyclo [2.2.1] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.2] octyl and bicyclo [3.2.1] octyl. In this context, an optionally substituted C ₃ -C ₈ -cycloalkyl is an optionally substituted C ₃ -C ₈ -cycloalkyl wherein one or more hydrogen atoms, for example 1, 2, 3, 4 or 5, hydrogen atoms are replaced by a substituent which is inert under the reaction conditions, Is intended to mean a cycloalkyl radical of 3 to 8 carbon atoms. Examples of inert substituents include CN, C ₁ -C ₆ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, and C ₁ -C ₄ -alkoxy- C ₁ -C ₆ -alkyl.

The term "optionally substituted C ₃ -C ₈ -cycloalkyl" refers to unsubstituted C ₃ -C ₈ -cycloalkyl as defined above, or one or more, for example 1, 2, 3 or 4, a C ₃ -C ₈ optionally substituted with-cycloalkyl, for example C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, phenyl or C ₃ -C ₆ - represents a cycloalkyl.

The term "optionally substituted phenyl ", as used herein, refers to unsubstituted phenyl or phenyl substituted with 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents which are inert under the reaction conditions . Examples of inert substituents include halogen, especially fluorine, chlorine or bromine, CN, NO _2, C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkylthio, C ₁ -C ₆ - alkylsulfonyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, and C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl.

The term as used herein, "optionally substituted phenyl, -C ₁ -C ₆ - alkyl" is C ₁ -C ₆ substituted by a one of a hydrogen atom, an optionally substituted phenyl - represents an alkyl. Examples include benzyl, 4-methylbenzyl, phenylethyl, and the like.

The term "optionally substituted phenyl" as used herein refers to unsubstituted phenyl or phenyl having 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents which are inert under polymerization conditions. Examples of inert substituents are halogen, especially fluorine, chlorine or bromine, CN, NO ₂ , C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and C ₃ -C ₆ -cycloalkyl.

The term as used herein "phenyl -C ₁ -C ₆ - alkyl", one of the hydrogen atoms are substituted with C ₁ -C ₆ group phenyl-represents an alkyl. Examples include benzyl, 4-methylphenyl, phenylethyl and the like.

As used herein, the term "optionally substituted phenyl-C ₁ -C ₆ -alkyl" refers to phenyl-C ₁ -C ₆ -alkyl as defined above, wherein the phenyl is unsubstituted or is 1 , two, three, four, five, in particular one, phenyl -C ₁ -C ₆ having the two or three substituents represents an alkyl. Examples of inert substituents are halogen, especially fluorine, chlorine or bromine, CN, NO ₂ , C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and C ₃ -C ₆ -cycloalkyl.

The method of the present invention comprises copolymerizing at least one silicon compound (SV) with at least one comonomer (CM).

Suitable silicon compounds (SV) are in particular compounds of the general formula I:

In the above general formula,

m is an integer from 1 to 11, in particular from 2 to 9, in particular 3,

x is 1, 2, 3 or 4, in particular 3 or 4,

R is optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₂ -C ₆ -alkenyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₃ -C ₆ -cycloalkyl, optionally substituted alkyl-phenyl, or optionally substituted phenyl C ₁ -C _6.

R in formula (I) is especially C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl, especially C ₁ -C ₄ -alkyl, when x is 1, 2 or 3.

Examples of compounds of formula I include the following compounds.

- (Compound of formula I wherein x = 4 and m = 3) and 1,1 ', 1 ", 1"' - silanetetrayltetrakis (azepan-

- 1, 1 ', 1''- (methyl silane tree-yl) tri (azepan-2-one) (= x = 3, R = CH 3 and m = 3 A compound of formula I).

Suitable silicon compounds (SV) also include oligomers comprising at least one repeating unit of the following general formula II:

m is an integer from 1 to 11, in particular from 2 to 9, in particular 3,

R 'is selected from the group consisting of optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₂ -C ₆ -alkenyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₃ -C ₆ -cycloalkyl, Substituted phenyl or optionally substituted phenyl-C ₁ -C ₆ -alkyl, or is a radical of formula A.

R 'in formula (II) is, in particular, a radical of formula (A), C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl, in particular of formula Radical; C ₁ -C ₄ -alkyl.

Oligomers comprising at least one repeating unit of the formula II may have not only the formula I but also at least one terminal group of the formula (IIa), and also a repeating unit of the formula (IIb) and / or a branching site of the formula (IIc) or have:

R 'in formulas (IIa) and (IIc) has the meaning given for formula (II), in particular radicals of formula (A), C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl, 9 and especially 3, or a radical of the formula (A); C ₁ -C ₄ -alkyl.

Of formula IIb R '' is an optionally substituted C ₁ -C ₆ - alkyl, optionally substituted C ₂ -C ₆ - alkenyl, optionally substituted C ₁ -C ₆ - alkoxy, optionally substituted C ₃ -C ₆ - Cycloalkyl, optionally substituted phenyl or optionally substituted phenyl-C ₁ -C ₆ -alkyl, especially C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl and especially C ₁ -C ₄ -alkyl.

Typical oligomers comprising at least one repeating unit of formula II typically contain an average (number) of 2 to 100, in particular 2 to 50, silicon atoms, with the proviso that, on average, Having at least one silicon atom. Oligomers of this type preferably comprise an average of at least 2, in particular 2 to 50, repeating units of formula (II).

The silicon compound (SV) used in the process of the present invention may also comprise a mixture of various compounds of formula I, or a mixture of one or more oligomers comprising a compound of formula I and a repeating unit of formula II .

The silicon compound (SV) used in the process of the present invention preferably comprises a compound of formula (I) or a mixture of various compounds of formula (I), especially a compound of formula (I) wherein x is 3 or 4, do.

Oligomers comprising the compounds of formula (I) and the repeating units of formula (II), as well as their preparation, are known or can be prepared, for example, as described in DE1247646, US3364160, US3417047, US4071498, DE2643467A1, DE3207336A1 and US4603177 or S. Andrianov et al. [Russ. Chem. Bull. 1972, 21, 1100-1102 (1977).

These are generally prepared by reacting one or more compounds of the formula VIII: < EMI ID =

R _{4 - x} SiCl _x (VIII)

In formula (VIII), R and x are each as defined above,

In the above general formula (III), m is as defined above and is particularly 2, 3 or 9, especially 3 in the presence of at least one base. The base is preferably used in a base in an amount of from 0.9 to 2 moles per mole of chlorine atoms in the compound of formula (VIII). Examples of suitable bases are in particular tertiary amines, especially tri-C ₁ -C ₄ -alkylamines and di-C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkylamines, such as triethylamine, , Dimethylisopropyl-amine, methyldiisopropylamine, tributylamine and dimethylcyclohexylamine, and also C ₁ -C ₄ -alkylimidazoles such as N -methylimidazole.

The reaction of the compound of formula (VIII) with the lactam of formula (III) generally takes place in the temperature range of -20 ° C to 110 ° C, preferably at 20 ° C to 30 ° C.

According to the present invention, the silicon compound (SV) is copolymerized with at least one comonomer selected from ammonium salts of dicarboxylic acids, amino-carboxylic acids and lactam.

According to the present invention, water is present for at least some time during copolymerization. Water plays a role in hydrolyzing the Si-N bond in the SV compound. This water can be formed by copolymerization itself, that is, when the CM comonomer includes at least one compound having a carboxyl group. In this case, the comonomer includes at least one compound selected from ammonium salts of dicarboxylic acids, aminocarboxylic acids and aminocarboxamides, and mixtures thereof. The water may also be added, especially if the monomer only contains a lactam.

The CM comonomer preferably comprises at least one monomer selected from ammonium salts of dicarboxylic acids, aminocarboxylic acids and aminocarboxamides, and mixtures thereof. In this way, copolymerization results in the formation of water, which in turn is capable of hydrolyzing the Si-N bond in the SV compound.

In one preferred embodiment, the CM comonomer is solely selected from at least one compound selected from ammonium salts of dicarboxylic acids, aminocarboxylic acids and minocarboxamides, and mixtures thereof. In a further preferred embodiment, the comonomer comprises at least one monomer selected from ammonium salts of dicarboxylic acids, aminocarboxylic acids and aminocarboxamides and mixtures thereof, and at least one lactam.

The total amount of water produced and / or added during the copolymerisation is preferably not less than 0.5 mol, in particular not less than 0.7 mol, in particular not less than 0.9 mol, of the lactam radical of the formula (A) attached to the silicon atom in the silicon compound (SV) . The total amount of water produced and / or added during the copolymerization is preferably not more than 2 mol, in particular not more than 1.5 mol, in particular not more than 1.1 mol, of the lactam radical of the formula (A) attached to the silicon atom in the silicon compound (SV) . This ensures complete conversion of the lactamyl-Si bond.

Suitable lactams are especially those of the formula III as defined above, especially those in which m in the formula III is 2-9, for example 2, 3 or 9, in particular 3. Examples of the lactam of formula (III) are ε-caprolactam, 2-piperidone (δ-valerolactam), 2-pyrrolidone (γ-butyrolactam), caprylactam, enantholactam and lauryllactam .

Suitable aminocarboxylic acids are especially those of the following formulas IV and V:

H ₂ N- (CH ₂ ) _y -COOH (IV)

H ₂ N-CHR ^x -COOH (V)

Y is an integer from 1 to 20, in particular from 2 to 12, for example 1, 2, 4, 5, 7, 9 or 11,

R ^x in formula (V) is optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₂ -C ₆ -alkenyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₃ -C ₆ -Cycloalkyl, optionally substituted phenyl or optionally substituted phenyl-C ₁ -C ₆ -alkyl, and in particular C ₁ -C ₄ -alkyl, phenyl or benzyl.

Examples of suitable aminocarboxylic acids of formula (IV) include glycine, 3-amino-propionic acid, 4-aminobutanoic acid, 5-aminovaleric acid, 6-aminocaproic acid, Acid, 12-aminododecanoic acid, 14-aminotetra-decanoic acid, 16-aminohexadecanoic acid and 18-aminooctadecanoic acid.

Examples of suitable aminocarboxylic acids of formula (V) are alanine, phenylglycine, valine, leucine, isoleucine and phenylalanine.

Suitable aminocarboxamides are in particular? -Aminocarboxamides, in particular the amides of the aminocarboxylic acids of the abovementioned formula (IV).

Suitable ammonium salts of dicarboxylic acids are in particular salts with dicarboxylic acids and diamines, in particular with aliphatic or cycloaliphatic dicarboxylic acids and aliphatic, cycloaliphatic, araliphatic or aromatic diamines. Typical dicarboxylic acids usually have 3 to 20, in particular 3 to 14, in particular 3 to 8 carbon atoms. The aliphatic dicarboxylic acid is the preferred dicarboxylic acid. Typical diamines usually have 2 to 12, in particular 3 to 14, in particular 3 to 8 carbon atoms. Salts of aliphatic diamines are preferred.

A particularly preferred ammonium salt of a dicarboxylic acid is a salt of a dicarboxylic acid of the formula (IV) < EMI ID =

HOOC- (CH ₂ ) _z -COOH (VI)

H ₂ N- (CH ₂ ) _v -NH ₂ (VII)

In the formula (VI), z is an integer of 1 to 12, particularly 1 to 4, and v in the formula (VII) is an integer of 2 to 12,

Examples of dicarboxylic acids of formula (VI) are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. Aromatic C _8-20 -dicarboxylic acids such as terephthalic acid and isophthalic acid may also be used.

Suitable diamines of formula VII include, for example, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine and decamethylenediamine. Hexamethylenediamine is particularly preferred.

The comonomer (CM) is preferably selected from the following:

b1) Aminocarboxylic acids, especially those of formula IV or V and especially those of formula IV;

b2) Salts of dicarboxylic acids with ammonium salts, especially with dicarboxylic acids and diamines, and especially with dicarboxylic acids of formula (VI) and diamines of formula (VII);

b3) At least one lactam, especially at least one lactam of the formula III, in particular caprolactam, especially a salt of a dicarboxylic acid and a diamine, and especially a salt of a dicarboxylic acid of the formula VI with a dicarboxylic acid of the formula VI and a salt of a diamine of the formula VII A mixture with a salt; And

b4) A mixture of at least one lactam, especially at least one lactam of the formula III, in particular caprolactam, with at least one aminocarboxylic acid, in particular at least one aminocarboxylic acid of the formula IV or V, and in particular at least one aminocarboxylic acid of the formula IV .

The comonomer (CM) is particularly preferably selected from comonomers of the groups b3) and b4) mentioned above, that is to say a mixture of at least one lactam and at least one aminocarboxylic acid, and also at least one lactam and at least one ammonium of the dicarboxylic acid ≪ / RTI > The molar ratio of the lactam to the aminocarboxylic acid or the ammonium salt of the lactam to the dicarboxylic acid is preferably 1.1: 1 or more, especially 2: 1 or more, particularly 1.1: 1 or more, in the groups b3) and b4) To 500: 1, in particular from 2: 1 to 100: 1.

The copolymerization of at least one silicon compound (SV) with at least one comonomer (CM) can be carried out similarly to a conventional method for producing a polyamide. Processes of this type are described, for example, in Kunststoff Handbuch, ¾ Technische Thermoplaste: Polyamide, Carl Hanser Verlag, 1998, Munich, 42-47 and 65-70.

The type and amount of the silicon compound (SV) provides specific control over the silicon content of the resulting composite material.

Preferably, the silicon compound (SV) is used in an amount of 0.1 to 70% by weight, in particular 0.5 to 50% by weight, in particular 1 to 25% by weight, based on the total amount of silicon compound (SV) do.

In a preferred embodiment of the process according to the invention, the silicon compound (SV) and the comonomer (CM) are present during the reaction in an amount of from 0.7 to 0.7 mol per mol of the lactam radical of formula (A) attached to the silicon atom in the silicon compound mol or more, or a substantial amount of water is added, wherein the amount of the material ratio is particularly preferably such that the amount of water generated / added is at least one of the amount of water added to the silicon atoms in the silicon compound (SV) Preferably not more than 2 mol, in particular 1.5 mol, and in particular 1.1 mol, per mol of the lactam radical of the formula (A). This ensures complete conversion of the lactamyl-silicon bond. More specifically, the silicon compound (SV) and the comonomer (CM) are reacted during the reaction with 0.7 to 2 mol of water per mol of the lactam radical of the formula (A) attached to the silicon atom in the silicon compound (SV) mol of water, in particular 0.9 to 1.1 mol of water, is used.

Such as aminocarboxylic acids, or ammonium salts of dicarboxylic acids, especially comonomers of group b1) or b2), or mixtures of the monomers of groups b3) and b4) mentioned above , These comonomers and the silicon compound (SV) preferably have a molar ratio of the carboxyl group in the comonomer to the lactam radical of the formula (A) attached to the silicon atom in the silicon compound (SV) of 0.7: In particular in the range of 0.9: 1 to 1.1: 1, in particular in the range of 0.7: 1 to 1.2: 1.

The copolymerization of at least one silicon compound (SV) with at least one comonomer (CM) can be carried out without the addition of a polymerization catalyst. The copolymerization can also be carried out in the presence of a polymerization catalyst. Typical polymerization catalysts include amidation catalysts that are used variously in the preparation of polyamides, examples of which include Bronsted acids such as hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid or sulfuric acid.

A typical procedure would be to heat a mixture of at least one silicon compound (SV) and at least one comonomer (CM) to the temperature required for polymerization. The temperature required for copolymerization naturally depends on the kind of the at least one silicon compound (SV) and the kind of at least one comonomer (CM), and can be determined by a routine method. The temperature required for the copolymerization is generally 100 ° C or higher, usually 120 ° C or higher or 150 ° C or higher, usually 320 ° C or lower, often 300 ° C or lower, particularly 280 ° C or lower. More particularly, the copolymerization is carried out at a temperature in the range of 150 ° C to 280 ° C, in particular in the range of 180 ° C to 260 ° C.

The method of the present invention can be carried out at atmospheric pressure, superatmospheric pressure or the system's native pressure. In general, the absolute pressure in the polymerization reactor is preferably in the range of about 1 to 70 bar, more preferably in the range of 1.0 to 20 bar.

At the start of the polymerization, the mixture may comprise the total amount of comonomer (CM) and the total amount of silicon compound (SV). However, it is also possible that one or more constituents of the mixture, preferably the comonomer (CM), are added in part to the mixture during the polymerization.

The copolymerization of at least one silicon compound (SV) with at least one comonomer is generally carried out as it is, that is, substantially in the absence of an inert diluent. The at least one silicon compound (SV) and at least one comonomer (CM) comprise at least 90 wt%, in particular at least 99 wt%, of the mixture used for the polymerization. However, the polymerization may be carried out in the presence of an inert diluent.

The copolymerization of at least one silicon compound (SV) with at least one comonomer can be carried out as a batch process or as a continuous process. Reactors suitable for ash or continuous copolymerization include reactors customary in the production of polyamides, as known to those skilled in the art. Continuous copolymerization is preferably carried out in a polymerization tube or in a polymer tube bundle. Specifically, a so-called VK tube is used for continuous copolymerization, where "VK" is German for " simplified continuous ".

The copolymerization can be designed as a one-step process or a multi-step process. In the case of multistage copolymerization, the first step involves the formation of an oligomer, which is then polymerized in another step to form the actual composite material. In the case of a multistage embodiment of continuous copolymerization, it is preferred that at least one of the steps be carried out in a VK tube. In the case of a multistage embodiment of continuous copolymerization, the first step can take place in a pressurized pre-reactor.

The composite material produced in the copolymerization may be subjected to one or more post-treatment steps, for example, extraction, drying, combination, molding or pelletization, or a combination thereof, to remove the non-converted monomer or oligomer.

The composite material produced in the copolymerization can be formed into, for example, one or more strands. Devices known to those skilled in the art may be used therefor. Perforated plates, die or die plates are examples of suitable devices. Preferably, the composite material produced in the copolymerization is formed into a strand in a flowable state and is pulverized into composite particles in the form of a flowable strand of reaction product. The hole diameter is preferably in the range of 0.5 mm to 20 mm, more preferably 1 mm to 5 mm, and most preferably 1.5 to 3 mm.

For pelletization, composite materials obtained by copolymerization and molded into one or more strands can be solidified and then pelletized. Suitable measures are described, for example, in Kunststoffhandbuch, 3/4 Technische Thermoplaste: Polyamide, Carl Hanser Verlag, 1998, Munich, pages 68-69. The underwater pelletization, which is also generally known to those skilled in the art, is one particular molding process.

Extraction of the composite material can be carried out similarly to extraction of polyamide. Methods and apparatus suitable for extraction of polyamides are generally known to those skilled in the art. Upon extraction, the levels of monomers and optional dimers and further oligomers in the composite can be reduced by treatment with an extractant. It can be achieved industrially, for example, by superheated steam (EP 0284968 W1) or by continuous or ash extraction into hot water (DE 2501348 A, DE 2732328 A). The extraction agent used preferably comprises water or consists of water. Suitable extraction agents also include mixtures of water and C ₁ -C ₄ -alkanols, such as water-ethanol mixtures. The extractant temperature is preferably in the range of 75 ° C to 130 ° C, more preferably 85 ° C to 120 ° C. Extraction can be carried out as a continuous process or as a batch process.

After extraction, the monomers or oligomers may be recovered from the extractant and used correspondingly in the preparation of polyamides or in the preparation of the composites according to the invention.

Preferably, the extracted composite material is subjected to a conventional drying process. For example, the extracted composite material can be dried by contacting it with dry air or a dry inert gas or a mixture thereof. An inert gas, such as nitrogen, is preferably used for drying. The extracted composite material may also be dried by contacting it with superheated steam or by contacting the mixture with a gas other than superheated steam, preferably an inert gas. Conventional driers such as countercurrent, cross flow, fan, tumble, paddle, trickle, cone or shaft drier, fluidized bed, etc. may be used. Ash drying in a tumble or cone dryer under reduced pressure is a suitable choice. Continuous drying in a drying tube where inert gas flows under drying conditions is another suitable choice. In one particular embodiment, at least one shaft drier is used for drying. Preferably there is a flow through a shaft dryer of hot gas which is inert under post polymerization conditions. Nitrogen is the preferred inert gas.

The composite material obtainable by the method of the present invention is not limited to the polyamides produced from the copolymerization of the comonomer (CM) with the lactam radical of the formula (A) present in the silicon compound (SV) Containing phase to form a dispersion. Depending on the type of silicon compound (SV), the silicon-containing phase is associated with a silicon dioxide phase or a polysiloxane phase, or a mixture of a silicon dioxide phase and a polysiloxane phase. The silicon dioxide phase is formed especially when the silicon atom in the silicon compound SV carries a lactam radical of formula A or only a lactam radical and an alkoxy radical of formula A while the polysiloxane phase is formed when the silicon atom in the silicon compound SV has a carbon atom ≪ / RTI > and the lactam radical of formula (A).

As mentioned, the silicon content of the polyamide composite material according to the present invention may be varied. The silicon content is generally in the range of 0.1 to 10.0 wt% (Si), especially 0.8 to 5.0 wt% (Si), based on the total weight of the composite material, in terms of silicon.

In the silicon-containing polyamide composite material of the present invention, the silicon-containing phase is finely dispersed in the polyamide matrix, wherein at least 90% of the SiO ₂ phase and / or polysiloxane phase are typically separated by SEM / EDX imaging or HAADF- Has a maximum domain size of 40 탆, especially 1 탆, and has a domain size usually in the range of 5 nm to 40 탆, preferably in the range of 10 to 1000 nm, in particular in the range of 20 to 500 nm.

Polyamide of the silicon-containing polyamide composite material of the present invention is usually from 15 000 ~ 50 000 range, especially 18 000-35 000 have a range of number average molecular weight (M _n). The weight average molecular weight (M _w ) of these polyamides is usually in the range of 40 000 to 225 000, especially 45 000 to 140 000. The molecular weight distribution of the polyamides is usually characterized by a polydispersity (= M _w / M _n ) in the range of 2.5 to 4.5, in particular in the range of 3 to 4.

The polyamide composite material of the present invention is generally obtained in the form of a powder or a pellet because of the production method thereof.

The silicon-containing polyamide composites of the present invention have a theoretical suitability in all applications in which polyamides are commonly used. The fields are in particular semi-fabricated products or plastic articles obtained from films, fibers, monofilaments, pipes, corrugated pipes, profiles, and also known and obtained through conventional molding / Manufacturing.

Hereinafter, the polyamide-silicon composite material of the present invention and the production thereof will be described in more detail with reference to Examples 1 to 4, Table 1 and Figs. 1 to 7. They are intended to illustrate some aspects of the invention and should not be construed as limiting the scope in any way.

1: ²⁹ Si- { ¹ H} -CP-MAS-NMR spectrum of the composite material of Example 4

2: ¹³ C- { ¹ H} -CP-MAS-NMR spectrum of the composite material of Example 4

3: DSC curve of the composite materials of Examples 1 to 4, second heating curve of periodic measurement, heating rate 10 K / min, 50 ml / min N ₂

4: ATR-FTIR spectra of the composites of Examples 1 to 4

5: SEM / EDX image of the platinum coated composite of Example 3

6: HAADF-STEM image of the composite material of Example 3 at various resolutions

7: EDX image of the platinum coated composite material of Example 1

<Abbreviation>

Smp .: Melting point

PMMA: Methyl methacrylate

HFIP: Hexafluoroisopropanol

DSC: Differential scanning calorimetry

GPC: Gel permeation chromatography

SEM: Scanning electron microscopy

EDX: Energy dispersive X-ray spectroscopy

ATR-FTIR: Attenuation Total Reflection Fourier Transform Infrared Spectroscopy.

<Analysis>

SEM / EDX images were recorded with the Nova NanoSEM 200 from FEI Company. The sample was coated with platinum before testing. Scale / magnification is specified in the drawing.

Solid state NMR spectroscopy of powder samples was performed on a Bruker Avance 400 spectrometer (frequency of ¹ H spectrum: 400.13 MHz, ¹³ C spectrum: 100.622 MHz) with a large diameter magnet and a dual resonance probe head. ¹³ C { ¹ H} -CP-MAS spectra were recorded using a 4 mm spinner vessel. Reference was made to adamantane (? = 38.5 ppm) as an external standard. ^The 29Si { ¹ H} -CP-MAS spectra were recorded using a 7 mm rotary vessel. Reference was made to tetrakistrimethylsilylsilane (? = -9.5 ppm) as an external standard.

DSC measurements were performed with a DSC1 instrument from Mettler Toledo. An aluminum crucible was used, and the crucible size was 40 mu l. Lt; RTI ID = 0.0 &gt; ml / min. &Lt; / RTI &gt; The heating rate was 10 K / min.

The molecular weight was determined by gel permeation chromatography (GPC). GPC measurements were performed using an Agilent 1100 Series instrument (HFIP-LG Guard, and PL HFIPGel) from Agilent Technologies, USA, with three columns. The eluent used was hexafluoroisopropanol (HFIP) + 0.05% CF ₃ COOK. Polymethylmethacrylate (PMMA) was used as standard. The measurement was performed under the following parameters: filtration through a column temperature of 40 ° C, flow rate of 1 ml / min, concentration of 1.5 mg / ml, Millipore Millex FG (0.2 μm).

The ATR-FTIR spectra were recorded using a FTIR spectrometer, FTS 165 from BIO-RAD, with Golden Gate fittings. The sample was applied directly to the measuring head and held in place by a sapphire anvil under a predetermined pressure of 5 bar. The measured data was recorded with a Win-IR program 1M, and evaluated using Origin.

Quantitative analysis of the elements C, H and N in the powder samples was carried out using a varioMICRO CHNS instrument from Elementar Analysensysteme GmbH. Reported values are the average of two measurements.

Manufacturing example

Example 1: A composite material having 1.8 wt% SiO ₂

The tank was charged with 15 g of epsilon -caprolactam, 3.3 g of omega -aminocaproic acid and 3.0 g of 1,1 ', 1 ", 1"' -silane tetrayltetrakis (azepan-2-one) Lt; / RTI &gt; The tank was then purged with argon three times. The tank was pressurized to about 10 bar (argon) for polymerization. The tank was heated to 230 캜 for about 1 hour and the stirrer was turned on at about 100 캜. The temperature of 230 DEG C was maintained for 2.5 hours. The pressure rose to about 15 bar during the reaction. In the last 15 minutes, the pressure was slowly reduced to atmospheric pressure.

After cooling, the composite material was extracted with methanol for 16 hours.

Smp. (DSC) 221 [deg.] C; Elemental analysis mass% (theory): C%: 61.0 (61.9), H%: 9.61 (9.64), N%: 11.8

Example 2: A composite material having 5.0 wt% SiO ₂

The tank was charged with 2.0 g of epsilon -caprolactam, 8.7 g of omega -aminocaproic acid and 9.3 g of 1,1 ', 1 ", 1"' -silane tetrayltetrakis (azepan-2-one) Lt; / RTI &gt; The tank was then purged with argon three times. The tank was pressurized to about 10 bar (argon) for polymerization. The tank was heated to 230 캜 for about 1 hour and the stirrer was turned on at about 100 캜. The temperature of 230 DEG C was maintained for 2.5 hours. The pressure rose to about 15 bar during the reaction. In the last 15 minutes, the pressure was slowly reduced to atmospheric pressure.

After cooling, the composite material was extracted with methanol for 16 hours.

The amount of extract was 12%.

Smp. (DSC) 220 [deg.] C; Elemental analysis mass% (theory): C%: 58.4 (58.3), H%: 9.24 (9.32), N%: 11.3 (11.3)

Example 3: Composite material having a 1.7% by weight of SiO ₂ /0.5% weight polysiloxane

The tank was charged with 15.0 g of epsilon -caprolactam, 3.9 g of omega -aminocaproic acid, 0.6 g of 1,1 ', 1 "- (methylsilanetriyl) tri (azepan- (A zepan-2-one) .The tank was then purged with argon three times.The tank was purged for about 10 bar (Argon) .The tank was heated to 230 DEG C for about 1 hour, the stirrer was turned on at about 100 DEG C, the temperature was maintained at 230 DEG C for 2.5 hours, the pressure rose to about 15 bar during the reaction, At 15 minutes, the pressure was slowly reduced to atmospheric pressure.

After cooling, the composite material was extracted with methanol for 16 hours.

A composite material having 1.7% by weight of SiO _{2 /} 0.5% by weight of polysiloxane was obtained.

Smp. (DSC) 221 [deg.] C; Elemental analysis mass% (theory): C%: 62.1 (61.3), H%: 9.79 (9.29), N%: 12.0

The GPC results are summarized in Table 1.

Example 4: Composite material having 4.0 wt% SiO ₂ / 1.1 wt% polysiloxane

The tank was charged with 6.0 g of epsilon -caprolactam, 11.9 g of omega -aminocaproic acid, 1.8 g of 1,1 ', 1 "- (methylsilanetriyl) tri (azepan- 1, 1 ', 1' ', 1' '' - silane tetrayltetrakis (azepan-2-one). The tank was then purged with argon three times. The tank was pressurized to about 10 bar (argon) for polymerization. The tank was heated to 230 캜 for about 1 hour and the stirrer was turned on at about 100 캜. The temperature of 230 DEG C was maintained for 2.5 hours. The pressure rose to about 15 bar during the reaction. In the last 15 minutes, the pressure was slowly reduced to atmospheric pressure.

After cooling, the composite material was extracted with methanol for 16 hours.

Smp. (DSC) 221 [deg.] C; Elemental analysis mass% (theoretical value): C%: 61.0 (58.7), H%: 9.62 (9.38), N%: 11.8

The GPC results are summarized in Table 1.

[Table 1]

GPC results of Examples 3 and 4; Eluent HFIP + 0.05% CF ₃ COOK, standard PMMA, column temperature 40 ° C

Description of Drawings:

Fig. 1 shows the ²⁹ Si- { ¹ H} -CP-MAS-NMR spectrum of the composite material of Example 4. Fig. From Figure 1 it is evident that the silicon dioxide network is verified by the Q signal at about -100 ppm and has polysiloxane units and is visible from the T signal at about -60 ppm.

Fig. 2 shows the ¹³ C- { ¹ H} -CP-MAS-NMR spectrum of the composite material of Example 4. Fig. In which the methyl groups of the polysiloxane reticular structure at about -7 ppm are visible as well as all the structural units of nylon-6 produced (methylene carbon at 25-50 ppm and carbonyl carbon at about 174 ppm).

Figure 3 shows a second heating curve of a periodic DSC measurement of the material after extraction. The resulting nylon-6 melts at about 220 ° C. The α-form as well as the γ-form are obvious.

The FTIR spectrum of Figure 4 shows characteristic bands of the resulting composite material. Si-O stretching vibration at about 1070 cm ^-1 , representing the SiO ₂ / polysiloxane network as well as the typical band or amide I and II bands for NH stretching vibration at nylon-6, for example about 3300 cm ^-1 Is also clear.

Fig. 5 shows an electron micrograph of the composite material of Example 3. Fig. In the selected image variant, silicon appears bright and other elements appear dark. Microscopic photographs show a relatively uniform distribution of silicon across the cross section of the sample.

6 shows an HAADF-STEM image of the composite material of Example 3. Fig. In this measurement method, the region rich in silicon appears brighter than the region less silicon. This image shows a relatively uniform distribution with respect to the silicon component. Primary particles of about 5 nm in size are present in larger aggregates.

EDX image of the platinum coated composite of Example 1. The elemental distribution of silicon in the composite material of Example 1 is visible in Fig. The resulting silicon dioxide is present in a relatively uniform distribution across the sample cross-section. The primary particles are partially agglomerated.

Claims (15)

A method for producing a silicon-containing polyamide composite material,
a. At least one silicon compound (SV) having at least one silicon atom containing at least one lactamyl radical attached through a nitrogen atom and having the formula (A)
b. At least one comonomer (CM) selected from an ammonium salt of a dicarboxylic acid, an aminocarboxylic acid, an aminocarboxamide and a lactam,
Wherein at least one comonomer (CM) is selected such that water is produced during copolymerization or water is added to the copolymerization reaction,

In the above formula, m is an integer of 1 to 11, particularly 2 to 9, and # is an attachment point to a silicon atom. The method according to claim 1, wherein the silicon compound (SV)
i) a compound of formula (I)
ii) an oligomer comprising repeating units of the formula (II), and
iii) a mixture of a compound of formula (I) and an oligomer comprising a repeating unit of formula (II)
&Lt; / RTI &gt;

In the above formula (I)
m is as defined in claim 1,
x is 1, 2, 3 or 4,
R is optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₂ -C ₆ -alkenyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₃ -C ₆ -cycloalkyl, optionally substituted phenyl or optionally substituted phenyl, -C ₁ -C ₆ - alkyl;

In the above formula (II)
m is as defined in claim 1 and R 'is a lactamyl radical of formula (A), or has one of the meanings specified for R in formula (I). 3. The method according to claim 1 or 2, wherein the silicon compound (SV) is a compound of formula (I) wherein x is 3 or 4. The method according to any one of claims 1 to 3, wherein the silicon compound (SV) and the comonomer (CM) are reacted with a lactam radical of formula (A) attached to a silicon atom in the silicon compound 0.7 mol or more per mole of water is produced or a substantial proportion of water is added. 5. The process according to any one of claims 1 to 4, wherein the copolymerization is carried out at a temperature in the range of from 150 ° C to 280 ° C. 6. Compounds according to any one of claims 1 to 5, wherein the comonomer is
b1) aminocarboxylic acid,
b2) an ammonium salt of a dicarboxylic acid,
b3) a mixture of at least one lactam and at least one ammonium salt of a dicarboxylic acid, and
b4) a mixture of at least one lactam and at least one aminocarboxylic acid
&Lt; / RTI &gt; 7. A composition according to any one of claims 1 to 6 wherein the comonomer used is a mixture of one or more lactam and one or more aminocarboxylic acids or a mixture of one or more lactam and one or more ammonium salts of dicarboxylic acids Way. 8. The process of claim 7, wherein the molar ratio of the lactam to the aminocarboxylic acid or the ammonium salt of the lactam to the dicarboxylic acid is at least 1.1: 1. 9. The method according to any one of claims 6 to 8, wherein the ammonium salt of the aminocarboxylic acid or the dicarboxylic acid and the silicon compound (SV) are selected so that the carboxyl group in the comonomer, the silicon atom in the silicon compound (SV) Wherein the molar ratio of the lactam radical of the formula (A) attached to the polymer is in the range of 0.9: 1 or more, particularly 0.9: 1 to 1.1: 1. 10. The method according to any one of claims 1 to 9, wherein the lactam used comprises a compound of formula (III)

In the above formulas, m is as defined in claim 1, in particular 2, 3 or 9, in particular 3. 11. The method according to any one of claims 1 to 10, wherein the aminocarboxylic acid is selected from compounds of the formulas (IV) and (V)
H ₂ N- (CH ₂ ) _y -COOH (IV)
H ₂ N-CHR ^x -COOH (V)
Y in the formula (IV) is 1 to 20,
Wherein R ^x is an optionally substituted C ₁ -C ₆ -alkyl, an optionally substituted C ₂ -C ₆ -alkenyl, an optionally substituted C ₁ -C ₆ -alkoxy, an optionally substituted C ₃ -C ₆ -alkoxy, ₆ -cycloalkyl, optionally substituted phenyl or optionally substituted phenyl-C ₁ -C ₆ -alkyl. 12. The process according to any one of claims 1 to 11, wherein the ammonium salt of the dicarboxylic acid is a salt of a dicarboxylic acid with a diamine, especially a dicarboxylic acid of the formula (VI) and a diamine of the formula (VII) &Lt; / RTI &gt;
HOOC- (CH ₂ ) _z -COOH (VI)
H ₂ N- (CH ₂ ) _v -NH ₂ (VII)
In the formula (VI), z is an integer of 1 to 12, particularly 1 to 4, and v in the formula (VII) is an integer of 2 to 12. A silicon-containing polyamide composite material obtainable by the method according to any one of claims 1 to 12. 14. The polyamide composite material of claim 13, comprising from 0.1 to 10.0 weight percent silicon based on the total weight of the composite material. A polyamide composite material according to claims 13 or 14 for the production of films, fibers, monofilaments, pipes and corrugated pipes, profiles, semi-fabricated products and plastic articles. Usage.

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